THERMAL PROPERTIES

OF POLYMERS

Presented By : P.Prabhu

Contents
Heat Capacity
Thermal Conductivity
Thermal Expansion
Glass Transition Temperature
Factors Affecting Tg

Heat Capacity
A solid materials potential energy is stored
as its heat energy.
Temperature of a solid is a measure its
potential energy.
Heat capacity is a property that is indicative
of a materials ability to absorb heat from
the external surroundings
It is defined as the amount of energy
required to produce a unit temperature rise.

Heat Capacity (Contd.)

Mathematically it is expressed as,

Where dQ is the energy required to produce

a temperature change equal to dT.
Heat capacity has units as J/mol-K or
Cal/mol-K.

Thermal Conductivity
Thermal conductivity is ability of a material to transport
heat energy through it from high temperature region to
low temperature region.
The heat energy, Q, transported across a plane of area A
in presence of a temperature gradient T/l is given by

where k is the thermal conductivity of the material.

It has units as W/m.K. It is a microstructure sensitive
property.

Thermal Conductivity
(Contd.)
Polymers are bad conductors. So, the calculation is
more experimental than theoretical.
Thus the two solutions to this problem can be
1. Extrapolation of melt data to a lower temperature
2.

Measurement of transient thermal behavior by

determining thermal diffusivity directly.

Factors Affecting TC:

Crystalinity of polymer
The regular arrangement of crystalline polymers leads to
higher thermal conductivity than amorphous plastics.
Conductivity decreases with increasing temp.

Fillers
Addition of more conductive polymer leads to increase in
conductivity
Air

or inert gas is added to produce foams which has

very low conductivity.

Factors Affecting TC:

Orientation
Orientation can either be along primary or secondary
bonds which link the polymers.
Very large changes in conductivity is observed when both
crystaitnity and orientation affects.

Pressure
Very minimal change is observed when a large change in
pressure is provided.

Thermal Expansion
Increase

in

temperature

may

cause

dimensional

changes.
Orientation of the sample espsiecally when crystalline
results in anisotropic expansion.
Linear coefficient of thermal expansion () defined as
the change in the dimensions of the material per unit
length.

Factors Affecting TE:

Crystallinity
Cross-linking
Fillers
Orientation

Glass Transistion Temp

Tg
The glass transition temperature is the property of the
amorphous region of the polymer,whereas the
crystalline region is characterized by the melting point.
The value of glass transition temperature is not unique
because the glassy state is not in equilibrium.
The value of glass transition temperature depends on
several factors such as molecular weight, measurement
method, and the rate of heating or cooling.

(Contd.)
The semi-crystalline polymer shows both the transitions
corresponding to their crystalline and amorphous regions.
Thus, the semi-crystalline polymers have true melting
temperatures (Tm) at which the ordered phase turns to
disordered phase, whereas the amorphous regions soften
over a temperature range known as the glass transition
(Tg).
It should be noted that amorphous polymers do not
possess the melting point, but all polymers possess the
glass transition temperature.

(Contd.)

(Contd.)
Glass Transition Temperatures of Some
Polymers
Polymer
Tg (C)
Polytetrafluoroethylene
97
Polypropylene (isotactic)
+100
Polystyrene
+100
Poly(methylmethacrylate) (atactic) +105
Nylon 6,6
+57
Polyethylene (LDPE)
120
Polyethylene (HDPE)
90
Polypropylene (atactic)
18
Polycarbonate
+150
Poly(vinyl acetate) (PVAc)
+28
Polyester(PET)
+69
Poly(vinyl alcohol) (PVA)
+85
Poly(vinyl chloride) (PVC)
+87

Factors Affecting Tg

I. Intermolecular Forces. Strong intermolecular forces cause

higher Tg. For example, PVC (Tg = 80 C) has stronger
intermolecular forces than polypropylene (Tg = 18 C)
because of the dipoledipole forces from the CCl bond.
II. Chain Stiffness. The presence of the stiffening groups
(such as amide, sulfone, carbonyl, p-phenylene etc.) in the
polymer chain reduces the flexibility of the chain, leading to
higher glass transition temperature. For example,
polyethyleneterephthalete is stiffer than polyethylene
adipate due to the presence of benzene ring .Therefore, Tg
value is higher for polyethyleneterephthalate.

Factors Affecting Tg

III. Cross-Linking. The cross-links between chains restrict

rotational motion and raise the glass transition temperature.
Hence, higher cross-linked molecule will show higher Tg
than that with lower cross-linked molecule.
IV. Pendant groups. The presence of pendent group can
change the glass transition temperature.
(a) Bulky pendant groups: the presence of bulky pendant
group, such as a benzene ring, can restrict rotational freedom,
leading to higher glass transition temperature. As in
polystyrene, the presence of benzene ring increases the Tg. In
polypropylene, there is no benzene ring that leads to lower Tg
Value.

Factors Affecting Tg
(b) Flexible pendant groups: the presence of flexible pendant
groups, for example, aliphatic chains, limits the packing of the
chains and hence increases The rotational motion, tending to
less Tg value. In polybutylmethacrylate, the
presence of large aliphatic chain reduces the Tg value when
compared with
that of polymethylmethacrylate.
V. Plasticizers. Plasticizers are low molecular weight and nonvolatile materials
added to polymers to increase their chain flexibility. They
reduce the intermolecular cohesive forces between the

Thank you.